Supplementary Figure S1 The excess loading of CO 2 on UTSA-16 and some MOFs synthesized in our lab at 296 K.

Transcription

1 CO 2 uptake (cm 3 (STP) cm -3 ) P (mmhg) UTS-16 UTS-15a Cu(DC-OH) UTS-25a UTS-2a Zn 5 (T) 6 (TD) 2 Zn 4 (OH) 2 (124-TC) 2 Y(PT) UTS-33a UTS-34 Supplementary Figure S1 The excess loading of CO 2 on UTS-16 and some MOFs synthesized in our la at 296 K. CH 4 uptake (cm 3 (STP) cm -3 ) UTS-16 UTS-15a Cu(DC-OH) UTS-25a UTS-2a Zn 5 (T) 6 (TD) 2 Zn 4 (OH) 2 (124-TC) 2 Y(PT) UTS-33a UTS P (mmhg) Supplementary Figure S2 The excess loading of CH 4 on UTS-16 and some MOFs synthesized in our la at 296 K.

2 Supplementary Figure S3 Comparison of the CO 2 /CH 4 adsorption selectivity of Cu-(py-1) 2 with that for the variety of MOFs considered in this work. In these calculations the partial pressures of CO 2 and CH 4 are taken to e eual to each other, i.e. p 1 = p 2. ll calculations are for 296 K. The calculations are ased on the Ideal dsored Solution Theory (IST) of Myers and Prausnitz. Supplementary Figure S4 Comparison of the CO 2 /N 2 adsorption selectivity of Cu-(py-1) 2 with that for the variety of MOFs considered in this work. In these calculations the partial pressures of CO 2 and N 2 are taken to e p 1 / p 2 =15/85. The calculations are ased on the Ideal dsored Solution Theory (IST) of Myers and Prausnitz.

3 Neutron Counts (x1) θ (deg) Supplementary Figure S5 NPD profiles for UTS-16 loaded with CO2. xperimental (circles), calculated (line), and difference (noisy line elow oserved and calculated patterns) at 5 K (space group I-42d). Vertical ars indicate the calculated positions of ragg peaks. λ=1.543å. Supplementary Figure S6 View of highly condensed CO2 packing in UTS-16. (a) From the c axe and () from the a axe.

4 Uptake (cm 3 (STP) cm -3 ) P (mmhg) Supplementary Figure S7 CO 2 sorption isotherms of the re-activated UTS-16. The repeated isotherms were measured at 296 K after the used UTS-16 was exposed in the air for 3 days, and then re-activated at 9 o C under high vacuum until the outgas rate is 5 µmhg min -1. The isotherms in the 1 st, 2 nd, 3 rd, and 4 th turns are respectively present as lack suare, red circle, green up triangle and lue down triangle.

5 Supplementary Tale S1 The surface area (S, m 2 /g), pore volume (cm 3 /g) and the calculated crystal density of activated samples (g cm -3 ) for the MOFs synthesized in our la. MOFs S T(Langmuir) Pore volume Framework density m 2 g -1 cm 3 g -1 g cm -3 References UTS (939) UTS-2a 1156 (1783) UTS-25a 994 (1461) Zn 4 (OH) 2 (1,2,4-TC) 2 48 (61) UTS-33a 66 (124) UTS (1533) Zn 5 (T) 6 (TD) (67) Cu(DC-OH) 397 (584) UTS-15a 553 (761) a.282 a Y(PT) 516 (798) Zn 4 O(FM) (1618) a) calculated from CO 2 sorption isotherm at 196 K. ) calculated from N 2 sorption isotherm at 77 K. Supplementary Tale S2 Structural data on the different MOFs evaluated in this study for CO 2 /CH 4 and CO 2 /N 2 separation for comparison purposes. MOFs Surface area Pore volume Framework density m 2 g -1 cm 3 g -1 g cm -3 MgMOF ZnMOF io-mof CuTC Cu-TDPT ZIF Zn(dc)(daco) MIL MOF

6 Supplementary Tale S3 Isotherm fit parameters for UTS-25a. CH 4 : p = 1+ p = 7 mol kg = = = 13.7 kj mol CO 2 : p = 1+ p = 2 mol kg = = = 22.2 kj mol

7 Supplementary Tale S4 Isotherm fit parameters for UTS-2a. CH 4 : p = 1+ p = 8.1mol kg = = = 29.2 kj mol CO 2 : p = 1+ p = 18mol kg = = = 32.4 kj mol

8 Supplementary Tale S5 Isotherm fit parameters for UTS-33a. CH 4 : +, p, p = + 1+ p 1+ p, = 3.3 mol kg, = 3.3 mol kg = = = 2.5 kj mol = = = 2.5 kj mol CO 2 : p = 1+ p = 6.2 mol kg = = = 3 kj mol

9 Supplementary Tale S6 Isotherm fit parameters for UTS-34. CH 4 : p = 1+ p = 6.8 mol kg = = = 2 kj mol CO 2 : p = 1+ p = 13.8 mol kg = = = 25.4 kj mol

10 Supplementary Tale S7 Isotherm fit parameters for UTS-15a. CH 4 : p = 1+ p = 14mol kg = = = 19.6 kj mol CO 2 : dual-site Langmuir fit was used. +, p, p = + 1+ p 1+ p, = 75mol kg, = 1.5 mol kg = = = = 23 kj mol = = 46.5 kj mol

11 Supplementary Tale S8 Isotherm fit parameters for Cu(DC-OH). CH 4 : p = 1+ p = 3.3 mol kg = = = 19.7 kj mol CO 2 : p = 1+ p = 4.6 mol kg = = = 27.7 kj mol

12 Supplementary Tale S9 Isotherm fit parameters for Y(PT). CH 4 : p = 1+ p = 8mol kg = = = 19.6 kj mol CO 2 : p = 1+ p = 11.2 mol kg = = = 2.3 kj mol

13 Supplementary Tale S1 Isotherm fit parameters for Zn 4 O(FM) 3. Note that the isotherm data for this MOF was otained ranging to pressures of 2.7 M. CH 4 : p = 1+ p = 21mol kg = = = 15.2 kj mol CO 2 : The isotherm was fitted with the dual-site Langmuir Freundlich isotherm. +, p = 2 1+ p 2, p + 1+ p, = 68.6 mol kg, = 1.1mol kg = = = = 42.4 kj mol = = 2 kj mol 6 2

14 Supplementary Tale S11 Isotherm fit parameters for Zn 4 (OH) 2 (1,2,4-TC) 2. CH 4 : p = 1+ p = 7.3mol kg = = = 16 kj mol CO 2 : p = 1+ p = 8.52 mol kg = = = 23 kj mol

15 Supplementary Tale S12 Isotherm fit parameters for Zn 5 (T) 6 (TD) 2. CH 4 : p = 1+ p = 1.8 mol kg = = = 22 kj mol CO 2 : dual-site Langmuir fit was used. Conseuently the isosteric heat of adsorption is a function of the loading. The value of Q st used for comparison with other MOFs corresponds with the loading that is in euilirium with ulk gas at 1 k. +, = 3.3 mol kg, = 1 mol kg = = = , p, p = + 1+ p 1+ p = 25 kj mol = = 4.6 kj mol

16 Supplementary Tale S13 Isotherm fit parameters for UTS-16. CH 4 : p = ; 1 + p = 9 mol kg ; = = = 15.6 kj mol CO 2 : dual-site Langmuir fit was used. +, p, p = + ; 1+ p 1+ p, = 5mol kg ;, = 3 mol kg = = = 33 kj mol ; = = = 48 kj mol N 2 : p = ; 1 + p = 12.7 mol kg ; = = = 12.3 kj mol

17 Supplementary Tale S14 Isotherm fit parameters for in CuTC. The measured experimental data on excess loadings pulished y Chowdhury et al. 41 on pure component isotherms for CO 2, and CH 4 at 295 K, 318 K, and 353 K in CuTC were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid phase molar densities within the pores. CO 2 : p = 1+ p = 18.2 mol kg = = = 25.5 kj mol CH 4 : p = 1+ p = 15.9 mol kg = = = kj mol

18 Supplementary Tale S15 Isotherm fit parameters for MIL-11. The measured experimental data on excess loadings pulished y Chowdhury et al. 41 on pure component isotherms for CO 2, and CH 4 at 295 K, 318 K, and 353 K in MIL-11 were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid phase molar densities within the pores. CO 2 : +, p, p = + 1+ p 1+ p, = 1 mol kg, = 45mol kg = = = 36 kj mol = = = 18 kj mol CH 4 : p = 1+ p = 34 mol kg = = = 9.9 kj mol

19 Supplementary Tale S16 Dual-site Langmuir-Freundlich parameter for adsorption of CO 2 in Zn(dc)(daco).5. These parameters were determined y fitting adsorption isotherm data reported in the work of experimental data of Mishra et al. 43 =, p 1+ ν p ν + i,, p 1+ ν p ν, = 6 mol kg, = 8mol kg = ν = 1 = = 18 kj mol = = = 48 kj mol ν = 1.88 ν

20 Supplementary Tale S17 1-site Langmuir parameters for pure CH 4 isotherms in Zn(dc)(daco) p = 1+ p = 22 mol kg = = = 13.3 kj mol

21 Supplementary Tale S18 Dual-site Langmuir parameter for adsorption of CO 2 and N 2 in Mg-MOF-74. These parameters were determined y fitting adsorption isotherms for temperatures ranging from 278 K to 473 K. The fit parameters are those reported earlier in the work of Mason et al. 17 CO 2 : +, p, p = + 1+ p 1+ p, = 6.8 mol kg ;, = 9.9 mol kg \ = = = 42 kj mol ; = = = 24 kj mol N 2 : Single-site Langmuir parameter for adsorption of N 2 in Mg-MOF-74. These parameters were determined y fitting adsorption isotherms for temperatures ranging from 293 K to 473 K. p = 1+ p = 14 mol kg = = = 18 kj mol

22 Supplementary Tale S19 Dual-site Langmuir parameter for adsorption of CH 4 in Mg-MOF-74. The CH 4 parameters were determined y fitting adsorption isotherm data reported in the work of Dietzel et al. 15 The reported excess loading data were converted to asolute loadings for fitting purposes. CH 4 : +, p, p = + 1+ p 1+ p = 11 mol ;, kg, = 5 mol kg = = = 2.5 kj mol ; = = = 16 kj mol

23 Supplementary Tale S2 Dual-site Langmuir-Freundlich parameters for pure component isotherms in Cu-TDPT. These fits are ased on experimental data of Li et al. 44. It is to e noted that for all guest molecules the experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.93 cm 3 /g, determined experimentally. Site Site i,, mol kg -1 i, ν i i, dimensionless CO i,, mol kg -1 i, ν i i, dimensionless CH N

24 Supplementary Tale S21 Dual-site Langmuir parameters for pure component isotherms in io-mof-11. These fits are ased on experimental data of n et al. 45. The experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.45 cm 3 /g, determined experimentally. Site Site i,, i, i, mol kg -1-1 dimensionless CO i,, i, i, mol kg -1-1 dimensionless N

25 Supplementary Tale S22 Dual-site Langmuir parameters for pure component isotherms in ZnMOF-74. These fits are ased on experimental data of Simmons et al. 46 comined with that of Yazaydin et al., 2 and Dickey et al. 47 The experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.58 cm 3 /g. Site Site i,, i, i, mol kg -1-1 dimensionless CO i,, i, i, mol kg -1-1 dimensionless N

26 Supplementary Tale S23 1-site Langmuir parameters for pure component isotherms in MOF-177 at 3 K. These are calculated using the T-dependent parameter values reported y Mason et al. 17 i,, i, i, -1 mol kg -1 dimensionless CO N Supplementary Tale S24 1-site Langmuir parameters for pure component isotherms in ZIF-78 at 296 K. These are otained y fitting the experimental isotherm data of anerjee et al. 28 The excess data were first converted to asolute loadings using the pore volume of.269 cm 3 /g. i,, i, i, -1 mol kg -1 dimensionless CO CH N

27 Supplementary Tale S25 Dual-site Langmuir parameter for adsorption of CO 2 in Cu-SSZ13. These fits are ased on experimental data of Hudson et al. 57. The experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.29 cm 3 /g, determined experimentally. +, p, p = + 1+ p 1+ p, = 6.8 mol kg, = 9.9 mol kg = = = 42 kj mol = = = 24 kj mol

28 Supplementary Tale S26 Dual-site Langmuir parameter for adsorption of CO 2 in H-SSZ13. These fits are ased on experimental data of Hudson et al.57. The experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.29 cm 3 /g, determined experimentally. +, p, p = + 1+ p 1+ p, = 6.8 mol kg, = 9.9 mol kg = = = 42 kj mol = = = 24 kj mol

29 Supplementary Tale S27 Single-site Langmuir parameter for adsorption of N 2 in Cu-SSZ13. These fits are ased on experimental data of Hudson et al. 57. The experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.29 cm 3 /g, determined experimentally. p = 1+ p = 48 mol kg = = = 1 kj mol

30 Supplementary Tale S28 Single-site Langmuir parameter for adsorption of N 2 in H-SSZ13. These fits are ased on experimental data of Hudson et al. 57. The experimentally determined excess loadings were first converted to asolute loadings using the Peng-Roinson euation of state for estimation of the fluid density. The pore volume used is.29 cm 3 /g, determined experimentally. p = 1+ p = 48 mol kg = = = 1 kj mol

31 Supplementary Tale S29 Dual-site Langmuir parameter for adsorption of CO 2 in NaX zeolite. These parameters were determined y fitting adsorption isotherm data reported in the works of elmakhout et al. 42 and Cavenati et al. 48, after converting the excess data to asolute loadings. +, p, p = + 1+ p 1+ p, = 3.5mol kg, = 5.2 mol kg = = = = 35 kj mol = = 35 kj mol

32 Supplementary Tale S3 Dual-site Langmuir parameter for adsorption of N 2 in NaX zeolite. These parameters were determined y fitting adsorption isotherm data reported in the works of elmakhout et al. 42 and Cavenati et al , p, p = + 1+ p 1+ p, = 3 mol kg, = 6mol kg = = = 13 kj mol = = = 13 kj mol

33 Supplementary Tale S31 Dual-site Langmuir parameter for adsorption of CH 4 in NaX zeolite. These parameters were determined y fitting adsorption isotherm data reported in the works of elmakhout et al. 42, after converting the excess data to asolute loadings. CH 4 : +, p, p = + 1+ p 1+ p = 4 mol ;, kg, = 5mol kg = = = 14 kj mol ; = = = 14 kj mol

34 Supplementary Tale S32 Dual-site Langmuir parameters for pure component isotherms in MFI. These fits are ased on CMC simulations that were carried out at 3 K. 49 Site Site i,, i, i, mol kg -1-1 dimensionless -6 1 CH N i,, i, i, mol kg -1-1 dimensionless Supplementary Tale S33 Single-site Langmuir parameters for pure component isotherms in JW. These fits are ased on CMC simulations that were carried out at 3 K. 49 i,, i, i, -1 mol kg -1 dimensionless CO CH N

35 Supplementary Tale S34 Isosteric heats (kj/mol) of adsorption for CO 2 and CH 4 in different MOFs. The loadings used in this comparison corresponds to that in euilirium with a ulk gas pressure of 1 k at 296 K. MOFs CO 2 CH 4 UTS UTS-2a UTS-33a UTS-15a Zn 5 (T) 6 (TD) Cu(DC-OH) UTS UTS-25a Zn 4 (OH) 2 (1,2,4-TC) Y(PT) Zn 4 O(FM)

36 Supplementary Tale S35 dsorption selectivities, and capacities, for euimolar CO 2 /CH 4 mixture at 2 k and 296 K in different MOFs and zeolites. CO 2 uptake CO 2 uptake CH 4 uptake MOFs or Zeolites capacity capacity capacity mol kg -1 mol L -1 mol kg -1 MgMOF UTS NaX zeolite CuTC JW Cu-TDPT UTS-2a UTS-25a Zn 4 (OH) 2 (1,2,4-TC) ZIF UTS UTS-33a Zn 5 (T) 6 (TD) MFI Cu(DC-OH) Zn(dc)(daco) UTS-15a MIL Zn 4 O(FM) Y(PT) S ads

37 Supplementary Tale S36 reakthrough calculations for a packed ed adsorer with inlet partial pressures of 2 k each of CO 2 and CH 4 mixture at 296 K and total pressures of 2 k. The reakthrough time corresponds to a gas composition contain.5 mole % CO 2 at the outlet. lso indicated are the numer of moles of CO 2 adsored during the time interval τ reak. MOFs or Zeolites Dimensionless reakthrough time CO 2 captured per kg of adsorent material during τ reak CO 2 captured per L of adsorent material during τ reak MgMOF NaX zeolite UTS JW CuTC Cu-TDPT UTS-2a ZIF UTS-25a UTS-33a Zn 4 (OH) 2 (1,2,4-TC) UTS Zn 5 (T) 6 (TD) Cu(DC-OH) MFI UTS-15a Zn(DC)(DCO) MIL Zn 4 O(FM) Y(PT)

38 Supplementary Tale S37 dsorption selectivities, and capacities, for 15/85 CO 2 /N 2 mixture at 1 k and 296 K in different MOFs and zeolites. CO 2 uptake CO 2 uptake N 2 uptake MOFs or Zeolites capacity capacity capacity mol kg -1 mol L -1 mol kg -1 MgMOF UTS NaX zeolite Cu-SSZ H-SSZ JW mmencuttri ZnMOF io-mof Cu-TDPT ZIF MFI MOF S ads

39 Supplementary Tale S38 reakthrough calculations for a packed ed adsorer with inlet partial pressures of 15 k and 85 k, respectively, for CO 2 and N 2 at 296 K. The reakthrough time corresponds to a gas composition contain.5 mole % CO 2 at the outlet. lso indicated are the numer of moles of CO 2 adsored during the time interval τ reak. MOFs or Zeolites CO 2 captured per kg of CO 2 captured per L of Dimensionless adsorent material during adsorent material during reakthrough time the time interval τ reak the time interval τ reak MgMOF NaX zeolite UTS Cu-SSZ H-SSZ JW mmencuttri ZnMOF Cu-TDPT io-mof ZIF MFI MOF

40 Supplementary Tale S39 The nearest O O distance (Å) etween the neighor CO 2 molecules trapped within the MOFs at the measurement temperature T (K). CO 2 loaded MOFs CCDC O O distance T (K) References [KCo 3 (C 6 H 4 O 7 )(C 6 H 5 O 7 )(H 2 O) 2 ].89CO This paper (C 6 H 6 N 8 O 4 Zn 2 ) 1.39CO (C 6 H 6 N 8 O 4 Zn 2 ) 1.3CO (C 6 H 6 N 8 O 4 Zn 2 ) 1.3CO (C 6 H 6 N 8 O 4 Zn 2 ) 1.3CO (C 32 H 24 Cu 2 N 2 O 8 ) 3CO (C 32 H 24 Cu 2 N 2 O 8 ) 2.97CO (C 32 H 24 Cu 2 N 2 O 8 ) 2.9CO (C 26 H 16 C l4 Co 3 N 8 O 2 ) C 3 H 8 NO C 2 H 8 N CO (C 8 H 2 Ni 2 O 6 ) 1.34CO (C 2 H 17 CuN 3 O 4 ) 2CO (C 3 H 3 MnO 6 ).25CH 2 O 2.5CO 2.67H 2 O (C 6 H 1 CuN 3 ).4CO (C 6 H 1 CuN 3 ) CO (C 6 H 1 CuN 3 ).42CO (C 6 H 1 CuN 3 ).25CO (C 6 H 1 CuN 3 ).8CO (C 3 H 3 lo).25ch 2 O 2.75CO 2.25H 2 O (C 3 H 3 GaO 6 ).25CH 2 O 2.75CO 2.25H 2 O (C 3 H 3 FeO 6 ).25CH 2 O 2.75CO 2.25H 2 O (C 3 H 3 InO 6 ).25CH 2 O 2.75CO 2.25H 2 O (C 35 H 3 N 2 O 8 Rh 2 ).111CO (C 32 H 24 N 2 O 8 Rh 2 ).73CO (C 34 H 28 N 2 O 8 Rh 2 ).75CO (C 34 H 28 N 2 O 8 Rh 2 ) 3CO disorder 9 81 (C 32 H 24 N 2 O 8 Rh 2 ).77CO

41 Supplementary References: 61. Guo, Z.-Y.; Wu, H.; Srinivas, G.; Zhou, Y.-M.; Xiang, S.-C.; Chen, Z.-X.; Yang, Y.-T.; Zhou, W.; O Keeffe, M. & Chen,. metal-organic framework with optimized open metal sites and pore spaces for high methane storage at room temperature. ngew. Chem. Int. d. 5, (211). 62. Chen, Z.-X.; Xiang, S.-C.; rman, H. D.; Li, P.; Zhao, D.-Y. & Chen,. Significantly enhanced CO 2 /CH 4 separation selectivity within a 3D prototype metal-organic framework functionalized with OH groups on pore surfaces at room temperature. ur. J. Inorg. Chem (211). 63. Zhang, Z.-J.; Xiang, S.-C.; Rao, X.-T.; Zheng, Q.; Fronczek, F. R.; Qian, G.-D. & Chen,. rod packing microporous metal-organic framework with open metal sites for selective guest sorption and sensing of nitroenzene. Chem. Commun. 46, (21). 64. He, Y.-.; Zhang, Z.-.; Xiang, S.-C.; Fronczek, F.-R.; Krishna, R. & Chen,. microporous metal-organic framework for highly selective separation of acetylene, ethylene, and ethane from methane at room temperature. Chem. ur. J. 18, (212). 65. He, Y.-.; Zhang, Z.-J.; Xiang, S.-C.; Wu, H.; Fronczek, F. R.; Zhou, W.; Krishna, R.; O Keeffe, M. & Chen,. High separation capacity and selectivity of C2 hydrocarons over methane within a microporous metal-organic framework at room temperature. Chem. ur. J. 18, (212). 66. Zhang, Z.-J.; Xiang, S.-C.; Chen, Y.-S.; Ma, S.-Q.; Lee, Y.; Phely-Roin, T. & Chen,. roust highly interpenetrated metal-organic framework constructed from pentanuclear clusters for selective sorption of gas molecules. Inorg. Chem. 49, (21). 67. Chen, Z.; Xiang, S.; rman, H. D.; Li, P.; Tidrow, S.; Zhao, D. & Chen,. microporous metal-organic framework with immoilized OH functional groups within the pore surfaces for selective gas sorption. ur. J. Inorg. Chem. 24, (21). 68. Chen, Z.-X.; Xiang, S.-C.; rman, H. D.; Mondal, J. U.; Li, P.; Zhao, D.-Y. & Chen,. Three-dimensional pillar-layered copper(ii) metal-organic framework with immoilized functional OH groups on pore surfaces for highly selective CO 2 /CH 4 and C 2 H 2 /CH 4 gas sorption at room temperature. Inorg. Chem. 5, (211). 69. Guo, Z.-Y.; Xu, H.; Su, S.-Q.; Cai, J.-F.; Dang, S.; Xiang, S.-C.; Qian, G.-D.; Zhang, H.-J.; O Keeffe, M. & Chen,. roust near infrared luminescent ytterium metal organic framework for sensing of small molecules. Chem. Commun. 47, (211). 7. Xue, M.; Liu, Y.; Schaffino, R. M.; Xiang, S.-C.; Zhao, X.; Zhu, G.-S.; Qiu, S.-L. & Chen,. New prototype isoreticular metal-organic framework Zn 4 O(FM) 3 for gas storage, Inorg. Chem. 48, (29). 71. Takamizawa, S.; Nakata,.; katsuka, T.; Miyake, R.; Kakizaki, Y.; Takeuchi, H.; Maruta, G. & S. Takeda, J. m. Chem. Soc. 132, (21). 72. Takamizawa, S.; Takasaki, Y. & Miyake, R. Chem. Commun (29). 73. Lin, J.-.; Xue, W.; Zhang, J.-P. & Chen, X.-M. Chem. Commun. 47, (211). 74. Dietzel, C. P. D.; Johnsen, R..; Fjellvag, H. ordiga, S.; Groppo,.; Chavan, S.; lom, R. Chem. Commun., (28). 75. Maji, T. K.; Mostafa, G.; Matsuda, R. & Kitagawa, S. J. m. Chem. Soc. 127, (25). 76. Cornia,.; Caneschi,.; Dapporto, P.; Faretti,. C.; Gatteschi, D.; Malavasi, W.;

42 Sangregorio, C. & Sessoli, R. ngew. Chem., Int. d. 38, (1999). 77. Zhang, J.-P. & Chen, X.-M. J. m. Chem. Soc. 131, (29). 78. Tian, Y.-Q; Zhao, Y.-M.; Xu, H.-J.; Chi, C.-Y. Inorg. Chem. 46, (27). 79. Takamizawa, S.; Kohara, M. Dalton Trans (27) 8. Takamizawa, S.; Nakata,.; Yokoyama, H.; Mochizuki, K. & Mori, W. ngew. Chem., Int. d. 42, (23). 81. Takamizawa, S.; Kojima, K.; katsuka, T. Inorg. Chem. 45, (26). 82. Takamizawa, S.; Nakata,.; Saito, T.; Kojima, K. CrystngComm 5, (23)